Catalyst for bisphenol compound production and process for producing bisphenol compound with the catalyst

ABSTRACT

Provided are a catalyst of high activity and good heavy substance resistance and alcohol resistance for production of bisphenols, and a method for producing bisphenols with the catalyst. The catalyst is a sulfonic acid-type cation-exchange resin modified with (a) a pyridinealkanethiol and (b) an aminoalkanethiol and/or a thiazolidine; and the method comprises reacting a phenol and a ketone in the presence of the catalyst for producing bisphenols.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a catalyst for production ofbisphenols, and to a method for producing bisphenols with the catalyst,and more precisely, it relates to a catalyst of high activity and goodheavy substance resistance and alcohol resistance for production ofbisphenols, and to a method for producing bisphenols with the catalyst.

[0003] 2. Description of the Related Art

[0004] It is known that bisphenol A [2,2-bis (4-hydroxyphenyl)propane]is an important compound for the starting material for engineeringplastics such as polycarbonate resins and polyarylate resins and alsofor epoxy resins, and the demand for it is much increasing these days.It is publicly known that bisphenols such as bisphenol A are produced byreacting phenols and ketones in the presence of a catalyst, acid-typecation-exchange resin. For it, it is also known to modify the catalyst,acid-type cation-exchange resin with a nitrogen-containing sulfurcompound for increasing the catalyst activity (e.g., JP-A 57-35533,6-340563, 10-251179).

[0005] However, the modification with a nitrogen-containing sulfurcompound has some drawbacks in that <1> if the degree of modificationwith it is high, the sulfonic acid points of the ion-exchange resin aredamaged and the resin activity is thereby lowered and <2> if the degreeof modification is high, heavy substances (side products in reaction)readily adhere to the pores of the ion-exchange resin to promote theresin degradation, but <3> if the degree of modification is low, alcoholin the starting material ketone promotes the resin degradation.

SUMMARY OF THE INVENTION

[0006] The present invention has been made in consideration of theviewpoint mentioned above, and it is to provide a catalyst of highactivity and heavy substance resistance and alcohol resistance forproduction of bisphenols, and to provide a method for producingbisphenols with the catalyst.

[0007] We, the present inventors have assiduously studied and, as aresult, have found that, when specific nitrogen-containing sulfurcompounds are combined for the modifier for the catalyst, ion-exchangeresin, then the object of the invention mentioned above can beeffectively attained. On the basis of this finding, we have completedthe present invention.

[0008] Specifically, the invention is summarized as follows:

[0009] 1. A catalyst for production of bisphenols, which is a sulfonicacid-type cation-exchange resin modified with (a) a pyridinealkanethioland (b) an aminoalkanethiol and/or a thiazolidine.

[0010] 2. The catalyst for production of bisphenols of above 1, in whichfrom 8 to 55% of the sulfonic acid group is modified.

[0011] 3. The catalyst for production of bisphenols of above 1 or 2, inwhich from 3 to 35% of the sulfonic acid group is modified with thecomponent (a).

[0012] 4. The catalyst for production of bisphenols of any of above 1 to3, which is for producing bisphenol A.

[0013] 5. A method for producing bisphenols, which comprises reacting aphenol and a ketone in the presence of the catalyst of any of above 1 to4.

[0014] 6. The method for producing bisphenols of above 5, wherein thephenol is unsubstituted phenol, the ketone is acetone and the bisphenolis bisphenol A.

[0015] 7. The method for producing bisphenols of above 6, wherein themethanol content of acetone is at most 3,000 ppm.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The invention is described in detail hereinunder.

[0017] In its first aspect, the invention provides a catalyst forproduction of bisphenols, which is a sulfonic acid-type cation-exchangeresin modified with (a) a pyridinealkanethiol (this may be referred toas a mercaptoalkylpyridine) and (b) an aminoalkanethiol (this may bereferred to as a mercaptoalkylamine) and/or a thiazolidine.

[0018] In its second aspect, the invention provides a method forproducing bisphenols, which comprises reacting a phenol and a ketone inthe presence of the catalyst.

[0019] Of the sulfonic acid-type cation-exchange resin (hereinafter thismay be abbreviated as ion-exchange resin), the matrix resin may be anyof styrene-divinylbenzene copolymers, perfluoroethylene copolymers,phenol-formaldehyde polymers and others, but preferred arestyrene-divinylbenzene copolymers. The resin may be gel or porous, butits degree of crosslinking is preferably low, for example, fallingbetween 2 and 8%. The mean particle size of the ion-exchange resin mayfall between 0.2 and 2.0 mm; and the particle size distributionuniformity may be broad, for example, falling between 1.0 and 1.6.

[0020] The modifier to modify the ion-exchange resin is a combination ofthe above-mentioned components (a) and (b).

[0021] The pyridinealkanethiol of the component (a) includes, forexample, 2-mercaptomethylpyridine, 3-mercaptomethylpyridine,2-mercaptoethylpyridine, 3-mercaptoethylpyridinne,4-mercaptoethylpyridine and their hydrochlorides. Of those, preferredare 4-mercaptoethylpyridine and its hydrochloride.

[0022] The aminoalkanethiol of the component (b) includes, for example,2-mercaptoethylamine, 3-mercaptopropylamine, 4-mercaptobutylamine andtheir hydrochlorides. Of those, preferred are 2-mercaptoethylamine andits hydrochloride.

[0023] The thiazolidine of the other component (b) includes, forexample, 2,2-dimethylthiazolidine, 2-methyl-2-ethylthiazolidine,cycloalkylthiazolidine, 2-methyl-2-phenylthioazolidine, and3-methylthioazolidine. Of those, preferred is 2,2-dimethylthiazolidine.

[0024] For modifying the ion-exchange resin, the modifier is dissolvedin a solvent that dissolves it and is selected, for example, from water,alcohols and ethers, and the resulting solution is gradually (within aperiod of from 20 minutes to 1 hour) added to the non-modifiedion-exchange resin that has been dispersed in the same solvent. Foruniform reaction (for uniformly converting the sulfone group of theresin into a modified group), the system is preferably stirred. Forfurther uniform reaction, the resin is modified in an aqueous solventthat contains acetic acid, monochloroaceic acid or trifluoroacetic acid.

[0025] For modifying the ion-exchange resin, the multiple components forthe modifier may be applied to the resin all at a time or may be appliedthereto one after another.

[0026] The reaction temperature may be room temperature or may be anelevated temperature (e.g., falling between 30 and 90° C.).

[0027] The amount of the modifier to be applied to the resin shall be socontrolled that the degree of modification with the component (a) mayfall between 3 and 35%, preferably between 5 and 30%, the degree ofmodification with the component (b) may fall between 5 and 52%,preferably between 5 and 30%, and the degree of total modification mayfall between 8 and 55%, preferably between 10 and 45%.

[0028] In the second aspect of the invention, bisphenols are producedthrough reaction of phenols and ketones in the presence of the modifiedion-exchange resin that serves as a catalyst.

[0029] Phenols must not have a para-positioned substituent relative tothe hydroxyl group therein. Concretely, they are unsubstituted phenol;alkylphenols such as o-cresol, m-cresol, o-tert-butylphenol,2,6-xylenol, 2,6-di-tert-butylphenol; and halogenophenols such aso-chlorophenol, m-chlorophenol, 2,6-dichlorophenol.

[0030] Concretely, ketones include acetone, methyl ethyl ketone, methylisobutyl ketone, methyl n-propyl ketone, acetophenone, cyclohexanone; aswell as aldehydes such as formalin, acetaldehyde, benzaldehyde.

[0031] The reaction mode is not specifically defined, but is preferablyfixed-bed continuous reaction or batch reaction. For example, when thereaction is fixed-bed continuous reaction, its liquid hourly spacevelocity (LHSV) generally falls between 0.1 and 30 hr⁻¹, but preferablybetween 0.3 and 10 hr⁻¹.

[0032] The reaction condition is described. The ratio of phenol toketone, phenol/ketone (by mol) generally falls between 3 and 30, butpreferably between 5 and 15.

[0033] The reaction temperature generally falls between 50 and 150° C.,but preferably between 60 and 110° C.

[0034] After the reaction, the non-reacted ketone, the produced waterand the excess phenol are removed, and the resulting concentrate iscooled to 10 to 20° C. whereby the adduct of bisphenol-phenol(hereinafter referred to as phenol adduct) is deposited. Next, phenol isevaporated away from the phenol adduct under reduced pressure (fallingbetween 100 and 700 Pa), and the residue is recrystallized from asuitable solvent to obtain the intended phenol product.

[0035] The method of the invention is favorable for production ofbisphenol A from starting compounds of acetone and phenol.

[0036] Preferably, the alcohol content (in which methanol is at least90% by mass) of acetone is at most 3,000 ppm, more preferably at most2,000 ppm, as too much alcohol in the starting compound may degrade thecatalyst.

EXAMPLES

[0037] The invention is described more concretely with reference to thefollowing Examples, which, however, are not intended to restrict thescope of the invention.

Example 1 <1> Preparation of Catalyst

[0038] In a 1000-cc flask, 200 cc of an ion-exchange resin (MitsubishiChemical's trade name, Diaion SK-104—this was swollen with water) and400 cc of methanol were stirred in suspension, to which was dropwiseadded a solution of 2.7 g of 4-mercaptoethylpyridine (this may bereferred to as 4-pyridine-ethanethiol, and will be hereinunderabbreviated as PET) in 50 cc of methanol within a period of 30 minutes.After the addition, this was stirred for 1 hour, and then theion-exchange resin was taken out through filtration, and washed twicewith 100 cc of ion-exchanged water. A part of the thus-separatedion-exchange resin was dried, and analyzed for acidity throughtitration. As a result, 8% of the acid points of the resin were modified(neutralized) with PET. Next, in a 1000-cc flask, the PET-modified resinand 400 cc of ion-exchanged water were stirred in suspension, to whichwas dropwise added a solution of 2.0 g of 2,2-dimethylthiazolidine(hereinafter this will be abbreviated as DMT) in 50 cc of ion-exchangedwater within a period of 30 minutes. After the addition, this wasstirred for 1 hour, and then the ion-exchange resin was taken outthrough filtration, and washed twice with 100 cc of ion-exchanged water.A part of the thus-separated ion-exchange resin was dried, and analyzedfor acidity through titration. 15% of the acid points of the resin weremodified (neutralized). This means that the degree of modification withDMT is 7%.

<2> Reaction

[0039] 69 cc of the PET/DMT-modified ion-exchange resin (swollen withwater) was filled in a stainless column, in which acetone was reactedwith phenol. The reaction temperature was 75° C.; and LHSV was 6 hr⁻¹(the acetone flow was 15 cc/hr, the methanol content of acetone was 300ppm, and the phenol flow was 277 cc/hr) The reaction result was asfollows: Just after the start of the reaction, the phenol conversion was10.3%. 400 hours after the start of the reaction, the phenol conversionwas 8.6%. Accordingly, the phenol conversion reduction rate was 1.7%/400hr.

Comparative Example 1 <1> Preparation of Catalyst

[0040] In the same manner as in Example 1, the ion-exchange resin wasmodified with PET alone. The degree of modification of the resin was 8%.

<2> Reaction

[0041] 69 cc of the PET -modified ion-exchange resin (swollen withwater) was filled in a stainless column, in which acetone was reactedwith phenol under the same condition as in Example 1. The reactionresult was as follows: Just after the start of the reaction, the phenolconversion was 9.5%. 400 hours after the start of the reaction, thephenol conversion was 5.4%. Accordingly, the phenol conversion reductionrate was 4.1%/400 hr.

Comparative Example 2 <1> Preparation of Catalyst

[0042] In the same manner as in Example 1, the ion-exchange resin wasmodified with DMT alone. The degree of modification of the resin was 7%.

<2> Reaction

[0043] 69 cc of the DMT-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 1. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 7.9%. 400 hours after the start of the reaction, the phenolconversion was 5.7%. Accordingly, the phenol conversion reduction ratewas 2.2%/400 hr.

Comparative Example 3 <1> Preparation of Catalyst

[0044] 50 cc of the PET-modified ion-exchange resin (swollen with water)that had been prepared in Comparative Example 1 and 50 cc of theDMT-modified ion-exchange resin (swollen with water) that had beenprepared in Comparative Example 2 were suspended in 200 cc ofion-exchanged water, and stirred for 20 minutes.

<2> Reaction

[0045] 69 cc of the mixture of the PET-modified ion-exchange resin(swollen with water) and the DMT-modified ion-exchange resin (swollenwith water) was filled in a stainless column, in which acetone wasreacted with phenol under the same condition as in Example 1. Thereaction result was as follows: Just after the start of the reaction,the phenol conversion was 8.8%. 400 hours after the start of thereaction, the phenol conversion was 5.3%. Accordingly, the phenolconversion reduction rate was 3.5%/400 hr.

Example 2 <1> Preparation of Catalyst

[0046] In a 1000-cc flask, 200 cc of an ion-exchange resin (MitsubishiChemical's trade name, Diaion SK-104—this was swollen with water) and400 cc of ion-exchanged water were stirred in suspension, to which wasdropwise added a solution of 1.8 g of 2-mercaptoethylamine (this may bereferred to as 2-aminoethanethiol, and will be hereinafter referred toas AET) in 50 cc of in-exchanged water within a period of 30 minutes.After the addition, this was stirred for 1 hour, and then theion-exchange resin was taken out through filtration, and washed twicewith 100 cc of ion-exchanged water. A part of the thus-separatedion-exchange resin was dried, and analyzed for acidity throughtitration. As a result, 10% of the acid points of the resin weremodified with AET. Next, in a 1000-cc flask, the AET-modified resin and400 cc of methanol were stirred in suspension, to which was dropwiseadded a solution of 5.0 g of PET in 50 cc of methanol within a period of30 minutes. After the addition, this was stirred for 1 hour, and thenthe ion-exchange resin was taken out through filtration, and washedtwice with 100 cc of ion-exchanged water. A part of the thus-separatedion-exchange resin was dried, and analyzed for acidity throughtitration. 25% of the acid points of the resin were modified. This meansthat the degree of modification with PET is 15%.

<2> Reaction

[0047] 69 cc of the AET/PET-modified ion-exchange resin (swollen withwater) was filled in a stainless column, in which acetone was reactedwith phenol. The reaction temperature was 75° C.; and LHSV was 6 hr⁻¹(the acetone flow was 15 cc/hr, the methanol content of acetone was 1000ppm, and the phenol flow was 277 cc/hr). The reaction result was asfollows: Just after the start of the reaction, the phenol conversion was11.7%. 400 hours after the start of the reaction, the phenol conversionwas 10.1%. Accordingly, the phenol conversion reduction rate was1.6%/400 hr.

Comparative Example 4 <1> Preparation of Catalyst

[0048] In the same manner as in Example 2, the ion-exchange resin wasmodified with AET alone. The degree of modification of the resin was10%.

<2> Reaction

[0049] 69 cc of the AET-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 2. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 8.2%. 400 hours after the start of the reaction, the phenolconversion was 5.8%. Accordingly, the phenol conversion reduction ratewas 2.4%/400 hr.

Comparative Example 5 <1> Preparation of Catalyst

[0050] In the same manner as in Example 2, the ion-exchange resin wasmodified with PET alone. The degree of modification of the resin was15%.

<2> Reaction

[0051] 69 cc of the PET-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 2. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 11.6%. 400 hours after the start of the reaction, the phenolconversion was 7.4%. Accordingly, the phenol conversion reduction ratewas 4.2%/400 hr.

Comparative Example 6 <1> Preparation of Catalyst

[0052] 50 cc of the AET-modified ion-exchange resin (swollen with water)that had been prepared in Comparative Example 4 and 50 cc of thePET-modified ion-exchange resin (swollen with water) that had beenprepared in Comparative Example 5 were suspended in 200 cc ofion-exchanged water, and stirred for 20 minutes.

<2> Reaction

[0053] 69 cc of the mixture of the AET-modified ion-exchange resin(swollen with water) and the PET-modified ion-exchange resin (swollenwith water) was filled in a stainless column, in which acetone wasreacted with phenol under the same condition as in Example 2. Thereaction result was as follows: Just after the start of the reaction,the phenol conversion was 10.1%. 400 hours after the start of thereaction, the phenol conversion was 7.0%. Accordingly, the phenolconversion reduction rate was 3.1%/400 hr.

Example 3 <1> Preparation of Catalyst

[0054] In a 1000-cc flask, 200 cc of an ion-exchange resin (MitsubishiChemical's trade name, Diaion SK-104—this was swollen with water) and400 cc of methanol were stirred in suspension, to which were dropwiseadded a solution of 6.6 g of PET in 50 cc of methanol and a solution of5.6 g of DMT in 50 cc of methanol within a period of 60 minutes. Afterthe addition, this was stirred for 1 hour, and then the ion-exchangeresin was taken out through filtration, and washed twice with 100 cc ofion-exchanged water. A part of the thus-separated ion-exchange resin wasdried, and analyzed for acidity through titration. The resin weremodified with PET by 20% and with DMT by 20%.

<2> Reaction

[0055] 69 cc of the PET/DMT-modified ion-exchange resin (swollen withwater) was filled in a stainless column, in which acetone was reactedwith phenol. The reaction temperature was 75° C.; and LHSV was 6 hr⁻¹(the acetone flow was 15 cc/hr, the methanol content of acetone was 2800ppm, and the phenol flow was 277 cc/hr). The reaction result was asfollows: Just after the start of the reaction, the phenol conversion was11.0%. 400 hours after the start of the reaction, the phenol conversionwas 9.0%. Accordingly, the phenol conversion reduction rate was 2.0%/400hr.

Comparative Example 7 <1> Preparation of Catalyst

[0056] In the same manner as in Example 3, the ion-exchange resin wasmodified with PET alone. The degree of modification of the resin was20%.

<2> Reaction

[0057] 69 cc of the PET-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 3. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 12.0%. 400 hours after the start of the reaction, the phenolconversion was 5.6%. Accordingly, the phenol conversion reduction ratewas 6.4%/400 hr.

Comparative Example 8 <1> Preparation of Catalyst

[0058] In the same manner as in Example 3, the ion-exchange resin wasmodified with DMT alone. The degree of modification of the resin was20%.

<2> Reaction

[0059] 69 cc of the DMT-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 3. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 8.8%. 400 hours after the start of the reaction, the phenolconversion was 5.0%. Accordingly, the phenol conversion reduction ratewas 3.8%/400 hr.

Comparative Example 9 <1> Preparation of Catalyst

[0060] 50 cc of the PET-modified ion-exchange resin (swollen with water)that had been prepared in Comparative Example 7 and 50 cc of theDMT-modified ion-exchange resin (swollen with water) that had beenprepared in Comparative Example 8 were suspended in 200 cc ofion-exchanged water, and stirred for 20 minutes.

<2> Reaction

[0061] 69 cc of the mixture of the PET-modified ion-exchange resin(swollen with water) and the DMT-modified ion-exchange resin (swollenwith water) was filled in a stainless column, in which acetone wasreacted with phenol under the same condition as in Example 3. Thereaction result was as follows: Just after the start of the reaction,the phenol conversion was 10.2%. 400 hours after the start of thereaction, the phenol conversion was 6.0%. Accordingly, the phenolconversion reduction rate was 4.2%/400 hr.

Example 4 <1> Preparation of Catalyst

[0062] In a 1000-cc flask, 200 cc of an ion-exchange resin (MitsubishiChemical's trade name, Diaion SK-104—this was swollen with water) and400 cc of methanol were stirred in suspension, to which was dropwiseadded a solution of 9.9 g PET in 100 cc of methanol within a period of30 minutes. After the addition, this was stirred for 1 hour, and thenthe ion-exchange resin was taken out through filtration, and washedtwice with 100 cc of ion-exchanged water. A part of the thus-separatedion-exchange resin was dried, and analyzed for acidity throughtitration. As a result, 30% of the acid points of the resin weremodified with PET. Next, in a 1000-cc flask, the PET-modified resin and400 cc of ion-exchanged water were stirred in suspension, to which wasdropwise added a solution of 2.8 g of DMT in 50 cc of ion-exchangedwater within a period of 30 minutes. After the addition, this wasstirred for 1 hour, and then the ion-exchange resin was taken outthrough filtration, and washed twice with 100 cc of ion-exchanged water.A part of the thus-separated ion-exchange resin was dried, and analyzedfor acidity through titration. 40% of the acid points of the resin weremodified. This means that the degree of modification with DMT is 10%.

<2> Reaction

[0063] 69 cc of the PET/DMT-modified ion-exchange resin (swollen withwater) was filled in a stainless column, in which acetone was reactedwith phenol. The reaction temperature was 75° C.; and LHSV was 6 hr⁻¹(the acetone flow was 15 cc/hr, the methanol content of acetone was 2000ppm, and the phenol flow was 277 cc/hr). The reaction result was asfollows: Just after the start of the reaction, the phenol conversion was10.8%. 400 hours after the start of the reaction, the phenol conversionwas 8.7%. Accordingly, the phenol conversion reduction rate was 2.1%/400hr.

Comparative Example 10 <1> Preparation of Catalyst

[0064] In the same manner as in Example 4, the ion-exchange resin wasmodified with PET alone. The degree of modification of the resin was30%.

<2> Reaction

[0065] 69 cc of the PET-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 4. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 11.8%. 400 hours after the start of the reaction, the phenolconversion was 6.6%. Accordingly, the phenol conversion reduction ratewas 5.2%/400 hr.

Comparative Example 11 <1> Preparation of Catalyst

[0066] In the same manner as in Example 4, the ion-exchange resin wasmodified with DMT alone. The degree of modification of the resin was10%.

<2> Reaction

[0067] 69 cc of the DMT-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 4. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 8.7%. 400 hours after the start of the reaction, the phenolconversion was 4.3%. Accordingly, the phenol conversion reduction ratewas 4.4%/400 hr.

Comparative Example 12 <1> Preparation of Catalyst

[0068] 50 cc of the PET-modified ion-exchange resin (swollen with water)that had been prepared in Comparative Example 10 and 50 cc of theDMT-modified ion-exchange resin (swollen with water) that had beenprepared in Comparative Example 11 were suspended in 200 cc ofion-exchanged water, and stirred for 20 minutes.

<2> Reaction

[0069] 69 cc of the mixture of the PET-modified ion-exchange resin(swollen with water) and the DMT-modified ion-exchange resin (swollenwith water) was filled in a stainless column, in which acetone wasreacted with phenol under the same condition as in Example 4. Thereaction result was as follows: Just after the start of the reaction,the phenol conversion was 10.0%. 400 hours after the start of thereaction, the phenol conversion was 5.2%. Accordingly, the phenolconversion reduction rate was 4.8%/400 hr.

Example 5 <1> Preparation of Catalyst

[0070] In a 1000-cc flask, 200 cc of an ion-exchange resin (MitsubishiChemical's trade name, Diaion SK-104—this was swollen with water) and400 cc of methanol were stirred in suspension, to which was dropwiseadded a solution of 3.3 g PET in 50 cc of methanol within a period of 30minutes. After the addition, this was stirred for 1 hour, and then theion-exchange resin was taken out through filtration, and washed twicewith 100 cc of ion-exchanged water. A part of the thus-separatedion-exchange resin was dried, and analyzed for acidity throughtitration. As a result, 10% of the acid points of the resin weremodified with PET. Next, in a 1000-cc flask, the PET-modified resin and400 cc of ion-exchanged water were stirred in suspension, to which wasdropwise added a solution of 2.8 g of AET in 50 cc of ion-exchangedwater within a period of 30 minutes. After the addition, this wasstirred for 1 hour, and then the ion-exchange resin was taken outthrough filtration, and washed twice with 100 cc of ion-exchanged water.A part of the thus-separated ion-exchange resin was dried, and analyzedfor acidity through titration. 25% of the acid points of the resin weremodified. This means that the degree of modification with AET is 15%.Next, the PET/AET-modified resin and 400 cc of ion-exchanged water werestirred in suspension in a 1000-cc flask, to which was added a solutionof 4.2 g of DMT in 50 cc of ion-exchanged water within a period of 30minutes. After the addition, this was stirred for 1 hour, and then theion-exchange resin was taken out through filtration, and washed twicewith 100 cc of ion-exchanged water. A part of the thus-separatedion-exchange resin was dried, and analyzed for acidity throughtitration. 40% of the acid points of the resin were modified. This meansthat the degree of modification with DMT is 15%.

<2> Reaction

[0071] 69 cc of the PET/AET/DMT-modified ion-exchange resin (swollenwith water) was filled in a stainless column, in which acetone wasreacted with phenol. The reaction temperature was 75° C.; and LHSV was 6hr⁻¹ (the acetone flow was 15 cc/hr, the methanol content of acetone was800 ppm, and the phenol flow was 277 cc/hr). The reaction result was asfollows: Just after the start of the reaction, the phenol conversion was10.2%. 400 hours after the start of the reaction, the phenol conversionwas 8.8%. Accordingly, the phenol conversion reduction rate was 1.4%/400hr.

Comparative Example 13 <1> Preparation of Catalyst

[0072] In the same manner as in Example 5, the ion-exchange resin wasmodified with PET alone. The degree of modification of the resin was10%.

<2> Reaction

[0073] 69 cc of the PET-modified ion-exchange resin (swollen with water)was filled in a stainless column, in which acetone was reacted withphenol under the same condition as in Example 5. The reaction result wasas follows: Just after the start of the reaction, the phenol conversionwas 9.8%. 400 hours after the start of the reaction, the phenolconversion was 5.5%. Accordingly, the phenol conversion reduction ratewas 4.3%/400 hr.

Comparative Example 14 <1> Preparation of Catalyst

[0074] In a 1000-cc flask, 200 cc of an ion-exchange resin (MitsubishiChemical's trade name, Diaion SK-104—this was swollen with water) and400 cc of ion-exchanged water were stirred in suspension, to which wasdropwise added a solution of 2.8 g AET in 50 cc of ion-exchanged waterwithin a period of 30 minutes. After the addition, this was stirred for1 hour, and then the ion-exchange resin was taken out throughfiltration, and washed twice with 100 cc of ion-exchanged water. A partof the thus-separated ion-exchange resin was dried, and analyzed foracidity through titration. As a result, 15% of the acid points of theresin were modified with AET. Next, in a 1000-cc flask, the AET-modifiedresin and 400 cc of ion-exchanged water were stirred in suspension, towhich was dropwise added a solution of 4.2 g of DMT in 50 cc ofion-exchanged water within a period of 30 minutes. After the addition,this was stirred for 1 hour, and then the ion-exchange resin was takenout through filtration, and washed twice with 100 cc of ion-exchangedwater. A part of the thus-separated ion-exchange resin was dried, andanalyzed for acidity through titration. 30% of the acid points of theresin were modified. This means that the degree of modification with DMTis 15%.

<2> Reaction

[0075] 69 cc of the AET/DMT-modified ion-exchange resin (swollen withwater) was filled in a stainless column, in which acetone was reactedwith phenol under the same condition as in Example 5. The reactionresult was as follows: Just after the start of the reaction, the phenolconversion was 8.3%. 400 hours after the start of the reaction, thephenol conversion was 5.8%. Accordingly, the phenol conversion reductionrate was 2.5%/400 hr.

Comparative Example 15 <1> Preparation of Catalyst

[0076] In the same manner as in Comparative Example 14, the ion-exchangeresin was modified with AET alone to prepare an AET-modifiedion-exchange resin. The degree of modification of the resin was 15%.Also in the same manner as in Comparative Example 14, the ion-exchangeresin was modified with DMT alone to prepare a DMT-modified ion-exchangeresin. The degree of modification of the resin was 15%. 50 cc of thePET-modified ion-exchange resin (swollen with water) that had beenprepared in Comparative Example 13, 25 cc of the above AET-modifiedion-exchange resin (swollen with water), and 25 cc of the aboveDMT-modified ion-exchange resin (swollen with water) were suspended in200 cc of ion-exchanged water, and stirred for 20 minutes.

<2> Reaction

[0077] 69 cc of the mixture of the PET-modified ion-exchange resin(swollen with water), the AET-modified ion-exchange resin (swollen withwater) and the DMT-modified ion-exchange resin (swollen with water) wasfilled in a stainless column, in which acetone was reacted with phenolunder the same condition as in Example 5. The reaction result was asfollows: Just after the start of the reaction, the phenol conversion was8.8%. 400 hours after the start of the reaction, the phenol conversionwas 5.0%. Accordingly, the phenol conversion reduction rate was 3.8%/400hr.

[0078] The catalysts prepared in the above are summarized in Table 1;and the test results obtained in the above are in Table 2. TABLE 1Modifier (degree of modification) Catalyst Component (a) Component (b)Morphology Example 1 PET (8%) DMT (7%) binary system Comp. Ex. 1 PET(8%) — single Comp. Ex. 2 — DMT (7%) single Comp. Ex. 3 PET (8%) DMT(7%) mixed system Example 2 PET (15%) AET (10%) binary system Comp. Ex.4 — AET (10%) single Comp. Ex. 5 PET (15%) — single Comp. Ex. 6 PET(15%) AET (10%) mixed system Example 3 PET (20%) DMT (20%) binary systemComp. Ex. 7 PET (20%) — single Comp. Ex. 8 — DMT (20%) single Comp. Ex.9 PET (20%) DMT (20%) mixed system Example 4 PET (30%) DMT (10%) binarysystem Comp. Ex. 10 PET (30%) — single Comp. Ex. 11 — DMT (10%) singleComp. Ex. 12 PET (30%) DMT (10%) mixed system Example 5 PET (10%) AET(15%) ternary system DMT (15%) Comp. Ex. 13 PET (10%) — single Comp. Ex.14 — AET (15%) binary system DMT (15%) Comp. Ex. 15 PET (10%) AET (15%)mixed system DMT (15%)

[0079] TABLE 2 Conversion Initial Conversion Reduction Methanol*Conversion after 400 Rate (%) (ppm) (%) hrs (%) per 400 hrs Example 1300 10.3 8.6 1.7 Comp. Ex. 1 300 9.5 5.4 4.1 Comp. Ex. 2 300 7.9 5.7 2.2Comp. Ex. 3 300 8.8 5.3 3.3 Example 2 1000 11.7 10.1 1.6 Comp. Ex. 41000 8.2 5.8 2.4 Comp. Ex. 5 1000 11.6 7.4 4.2 Comp. Ex. 6 1000 10.1 7.03.1 Example 3 2800 11.0 9.0 2.0 Comp. Ex. 7 2800 12.0 5.6 6.4 Comp. Ex.8 2800 8.8 5.0 3.8 Comp. Ex. 9 2800 10.2 6.0 4.2 Example 4 2000 10.8 8.72.1 Comp. Ex. 2000 11.8 6.6 5.2 10 Comp. Ex. 2000 8.7 4.4 4.3 11 Comp.Ex. 2000 10.0 5.2 4.8 12 Example 5 800 10.2 8.8 1.4 Comp. Ex. 800 9.85.5 4.3 13 Comp. Ex. 800 8.3 5.8 2.5 14 Comp. Ex. 800 8.8 5.0 3.8 15

[0080] As described in detail hereinabove with reference to itspreferred embodiments, the invention provides a catalyst of highactivity and good heavy substance resistance and alcohol resistance forproduction of bisphenols, and to a method for producing bisphenols withthe catalyst.

What is claimed is:
 1. A catalyst for production of bisphenols, which isa sulfonic acid-type cation-exchange resin modified with (a) apyridinealkanethiol and (b) an aminoalkanethiol and/or a thiazolidine.2. The catalyst for production of bisphenols as claimed in claim 1, inwhich from 8 to 55% of the sulfonic acid group is modified.
 3. Thecatalyst for production of bisphenols as claimed in claim 1 or 2, inwhich from 3 to 35% of the sulfonic acid group is modified with thecomponent (a).
 4. The catalyst for production of bisphenols as claimedin any of claims 1 to 3, which is for producing bisphenol A.
 5. A methodfor producing bisphenols, which comprises reacting a phenol and a ketonein the presence of the catalyst of any of claims 1 to
 4. 6. The methodfor producing bisphenols as claimed in claim 5, wherein the phenol isunsubstituted phenol, the ketone is acetone and the bisphenol isbisphenol A.
 7. The method for producing bisphenols as claimed in claim6, wherein the methanol content of acetone is at most 3,000 ppm.